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The many flavours of mechanochemistry and its plausible conceptual underpinnings

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NATURE REVIEWS CHEMISTRY
卷 5, 期 3, 页码 148-167

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NATURE PORTFOLIO
DOI: 10.1038/s41570-020-00249-y

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Mechanochemistry involves diverse phenomena where mechanical load influences chemical reactions, such as motor protein function, organic synthesis in a ball mill, reactions at a propagating crack, chemical actuation, and polymer fragmentation. The rate of deformation in mechanochemistry affects which and how many bonds break, either powering macroscopic motion in otherwise endergonic reactions or being driven by spontaneous chemical reactions. The complexity of mechanochemistry lies in the dynamic coupling between inertial motion at the microscale and changes in chemical bonding across multiple length scales and timescales.
Mechanochemistry describes diverse phenomena in which mechanical load affects chemical reactivity. The fuzziness of this definition means that it includes processes as seemingly disparate as motor protein function, organic synthesis in a ball mill, reactions at a propagating crack, chemical actuation, and polymer fragmentation in fast solvent flows and in mastication. In chemistry, the rate of a reaction in a flask does not depend on how fast the flask moves in space. In mechanochemistry, the rate at which a material is deformed affects which and how many bonds break. In other words, in some manifestations of mechanochemistry, macroscopic motion powers otherwise endergonic reactions. In others, spontaneous chemical reactions drive mechanical motion. Neither requires thermal or electrostatic gradients. Distinct manifestations of mechanochemistry are conventionally treated as being conceptually independent, which slows the field in its transformation from being a collection of observations to a rigorous discipline. In this Review, we highlight observations suggesting that the unifying feature of mechanochemical phenomena may be the coupling between inertial motion at the microscale to macroscale and changes in chemical bonding enabled by transient build-up and relaxation of strains, from macroscopic to molecular. This dynamic coupling across multiple length scales and timescales also greatly complicates the conceptual understanding of mechanochemistry.

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